Alkadienedioate-fumarate adducts, method of making, and polyvinyl chloride plasticized therewith



ALKADIENEDIOATE FUMARATE ADDUCTS, METHOD or MAKING, AND. POLYVINYL CHLORIDE PLASTICIZED Joachim Dazzi, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo;, a corporation of law e No Drawing. Application May '13, 1957 Serial No. 658,509

'1 Claims- 260 -4 -3) The present invention relates to adducts and more particularly provides new 'polycarboxylates, methods ofpreparing the same, and vinyl chloride polymers 'plastici'zed with the polycarboxylates.

According to the invention there are provided adducts in which from 1 to. 6 moles of an alkyl orallgoxyalkyl fumarate having from 1 to 8 carbon atoms in each alhyl or alkoxyalkyl radical is combined at the 'long =chain, s s p t o of a n-c j a e di ky alkadi ns: dioate having from 1 to 8 carbon atoms in each alkyl radical and from 20 to 30 carbon atoms in the acyl port on o h oa Such. ad u ha e t e. probabl formula:

ROOC-Y-COOR in which R is an alkyl radical of from 1 to 8 carbon atoms, Z is selected from the class consisting of R and alkoxyalkyl radicals of from 1 to 8 carbon atoms; Y is an aliphatic, non-conjugated, diolefinic hydrocarbon radical or from 18 to 28 carbon atoms,- aridn is anumber offromlto6.

Polycarboxylates having the above formula may be readily prepared by heating the appropriategfdialleyl or bis(alkoxyalkyl) fumarate *a dialkyl'ester ofanaliphatic, non-conjugated :diolefinic, dicarboxylic acid of from 20 to 30 carbon. atoms wherein the alkyl radicals have from 1 to 8 carbon atoms. The diolefinic carboxylic acid may be straight chained or branched.

Presently useful diolefinic esters are, -e.g., the simple diesterssuch as diethyl or di-n-p'ropyl 8",12-eicosadiene? dioate; dimethyl or di-n-butyl heneicosadienedioate; biS(2T-r ethylhexyl) or diisopropyl 2,l7-dimethyloctadecadiene-. dioate; dioctyl or di-n-amyl docosadiened-ioate; di-n-butyl or di-tert-amyl tricqsadienedioate; diisobutyl or diethyl tetracosadienedioate; dihexylor diethyl 11-vinyl-8-octadienedioate; diisoamyl or di-tert-butyl heptacosadienedioate; di-n-octyl or dimethylnonacosadienedioate; diethyl or di-n-butyl triacontadienediOatQ; and themixed olefinic diesters such as n-butyl isopropyl 8,12-eicosa ene dioate; ethyl y y & -ciso a isne lioa e;jo amyl n-butyl docosadienedioate The olefinicdouble bonds in the useful dienedioates must be non-conjugated.

Fumarates which are condensed with said higher olefinic acid esters are the simple diesters such as methyl, amyl, ethyl, isohexyl, n-heptyl, n-propyl, n-octyl, 2-ethylh yl, u yl -et xy hy -me o ypr pyh 4: butoxybutyl, 3-ethoxypropyl, S ethoXyamyI, o'r' property-i methyl fumarate and the mixed esters su h. as ethyl Propyl fumarats, isobutyl msthyllifumara c ethy m hy fumarate, nhexyl isopropyl fumarate, n-butyln-"octyl fumarate, 2 ethyloxyethyl "'propyl funiaratefB-butoxypropyl ethyl fumarate, Z-aniyloxyethyl 3-propoxypropyl fumarate, etc. t a

Reac on of. the. di asd oateu ththefumarat is ,sfie t sl by simply healing'a mixture of the two reactants at tem- 2,909,500 i Patented 06$. .20, 1,959

peratures offrom, say, 100 C. to 3.00 0., depending upon the nature of the individual reactants and of the properties desired in the final product. The reaction is generally elfected at atmospheric pressure, but. pressures below atmospheric or above atmospheric may be lSfid. Condensation catalysts may be employed. The reaction results in the addition of from l to 6 moles ofthe futnarate at the long chain dienic portion f he dimedioate. Thus the reaction of. a simple dialkyl fumarate such as methyl fumarate with an ester like the nonconjugated dibutyl eicosadienedioate can-yield adducts in which from 1 to3 moles of the fumarateihave f r lcted with the dienedioate, depending upon the reaction time and the proportion of reactants used:

CHICCHQSOQ C-Y-0 0 ownmon, 1101130 0 O.CH

' ,E-Q 'QQ s OHA HMO00-Y-Q0 'ZQ aQ a 3 16 1 11:] Q ongcooons in wh h Y is a nonju d alkadienyl a c l carbon atoms, and n is an integer of from 1 to, 6. The, present adducts are stable, high-boiling, clear and bstant al y sp s p duc s ch range Qm v co s iq ds t semi-so id. masse he m y be ad n a; ously e p o ed or a a ety t in u tri Pu ses. s ubr can add s. a fu s a xflu da s inter ed ates. o t e pr duc i n of fac -a e agstit t ta, They, are, p rt cul r y va uabl as p a i zer o v nyl chloride po ymers, the. p at cs s er in no Qnly'm wh n viny hloride polymers. bu lso o imp r s mu i t n cus y a h h. de ree of low mpe a r fle ibi ty; Ve see ,v mper ure ta ility, nd e t me hanica strength to these polymers. They are compatible' withi vinyl chloride polymers and show no exudation of plasti-' cizer even at plasticizer content of up to 50 percent. Although the quantity of .plasticizer will .dependmpon 'the particular polymer tobe plasticized anduponi its molecus. lar weight, it is generally found thattcompositionshaving from 5 percentby weightof plasticizer'wilhein most cases, be satisfactory. for general: utility. Thecgoodlfiexir. bility of the plasticized compositions increases with in-v creasing plasticizer concentration. 7 e The present polycarboxylates are valuable plasticizers for polyvinyl chloride and copolymers'of. at; least-.71)- percent by weight of an unsaturated monomer 'copolys; merizabletherewith, for example, vinyl'ace'tate, vinylidenechloride, etc.-

The'invention is further illustrated, but not limited;

g the following examples:

Example 1 1,12-eicosadienedioic acid (obtained; from Shell-Ber: velopment Co.)-was convertedinto the dibutyl ester. by; heating a mixture consisting of g. ,(:0.44;-'mole). of said acid, 3 moles of n-butanol and 0.5 g. ofp -toluene sulfonic acid at a pot temperature of 1l 0l2,0* C. for; 1.5 hours while collecting the by-product water in a than. which 'formedpart of the reaction equipment. At: end of this time 17 ml. of water had collected. Aiteig washing with water and neutralizing with'sodium'hydroxidethe product was distilled to give l98' g.;ol?. the substantially pure di-n-butyl 1 ,l2-eicosadienedioate, 3:1 230-245" C. /1.2-l .5 mm.,' 11 1.4574, freezing at about 11 C.

butyl fur'narate as follows;

' 'lo a flask equippedwith a reflux condenser and stirrer" there were charged 112.5 g. (0.25 mole) of said di n j nitrogen atmosphere for about eight hours at a temperature of about 240 to 242 C. Distillation of the resulting reaction product at a pressure of 1 mm. mercury and also in a nitrogen atmosphere gave 80.7 g. of a fraction B.P., 160 C./1 mm. (mostly 1l0-116 C.) compris ing di-n-butyl furnarate; 27.8 g. of a fraction, B.-P. 160- 180 C./1 mm. comprising dimeric di-n-butyl fumarate; and, as residue, 276 g. of a viscous product, 11 114660, having a saponification equivalent of 144, an iodine number of 36.5 and 36.0 on two diiferent determinations, and a freezing point of minus 50 C. Based on the recovered butyl furnarate and dimer and on the found saponification equivalent, the residue is an adduct in which one mole of the di-n-butyl 8,12-eicosadienedioate is combined with an average of three moles of di-n-butyl fumarate, the calculated saponification value of the 1:3 dienedioatefumarate adduct being 141.5.

Example 2 Sixty parts by weight of polyvinyl chloride and 40 parts by weight of the 1:3 dienedioate-fumarate adduct of Example l'were' mixed together on a rolling mill to a homogeneous blend. During the milling there was observed substantially no fuming and discoloration. A molded sheet of the mixture was clear and transparent and substantially colorless/ Testing of the molded sheet for low temperature flexibility by the Clash-Berg method gave a value of minus-26.7 C. Testing of the volatility characteristics of the plasticized composition by a modified carbon absorption test procedure of the Society of Plastics Industry gave a volatility value of 0.9 percent, which value shows very good temperature stability of the plasticizer composition. A sample of the plasticized composition which had been immersed in distilled water for 24 hours showed a solids loss of 0.12 percent, and immersion of a disc of the plasticized composition in kerosene for 24 hours gave a kerosene extraction value of 4.5 percent, which value indicates very good kerosene resistance.

I V: Example3 A mixture consisting of 22.5 g. (0.05 mole) of the din-butyl 1,12-eicosadienedioate of Example 1 and .70 g. (0.28.mole.) of bis(2-ethoxyethyl) fumarate was heated for 6 hours at a temperature of 250 C. ina nitrogen atmosphere. Distillation of the resulting reaction prodnot at an oil bath temperature of 250 C. and a pressure of 1.2 mm. removed 4.1 g. of distillate, n 1.4484, which was: mostly vunreacted. fumarate. There was thus with 60 parts by weight of a vinyl chloride-vinyl acetate copolymer known to the trade as Vinylite, there are obtained clear, colorless compositions of very good flexibility and stability.

While the above examples show only a composition in which the ratio of plasticizer to polymer content is :60, the ratio of dienedioate-fumarate adduct to polyvinyl chloride may be widely varied, depending upon the properties desired in the final product. For many purposes, an adduct content of, say, from only 10 percent to 20 percent is preferred. Although the invention has been described particularly with reference to the use of the present adducts as plasticizers forpolyvinyl chloride, these polycarboxylates are advantageously employed also as plasticizers for copolymers of vinyl chloride, for example, the copolymers of vinyl chloride with vinyl' fluoride, vinylidene chlorofluoride, vinylidene chloride, methyl methacrylate, acrylonitrile, etc. Preferably, such copolymers have a high vinyl content, i.e., a vinyl chloride content of at least 70 percent of vinyl chloride and up to 30 percent by weight of the copolymerizable monomer.

The plasticized polyvinyl halide compositions of the present invention have good thermal stability; however, for many purposes it may be advantageous to use known stabilizers in the plasticized compositions. Also, while the present adducts are of general utility in softening vinyl chloride polymers, they may be used as the only plasticizing component in a compounded vinyl chloride polymer, or they may be used in conjunction with other plasticizers.

What I claim is:

1. An adduct of the formula ROOC-Y-COOR [iHOOOZ in which R is an alkyl radical of from 1 to 8 carbon atoms, -Z'is selected from the class consisting of R and obtained as residue 87g. of. the very viscous substantially 7 pure adduct, n 1.4676, i.e., an adduct in which one moleof the di-n-butyl 1,12-eicosadienedioate has combined with an average of 4.96 moles of the bis(ethoxyethyl) fumarate. value of 140, as compared to 145.1, the calculated value. Two grams of said adduct were added to 30 grams of a 10 percent solution of polyvinyl chloride in cyclohexanone. The solution of polyvinyl chloride-adduct mixture thus obtained contained 40 parts by weight of adduct per 60 parts by weight of polyvinyl chloride. A film cast from the solution was'clear and flexible and entirely compatible. Inspection of said film after storage for one week at ordinary atmospheric conditions revealed no exudation of adduct or any change in color and flexibility of the film.

' .Instead of =.the di-n-butyl 8,12-eicosadienedioate-di-nbutylfumarate or 2-.ethoxyethyl. adducts of Examplesl. and.3,,.oth'er higher non-conjugated dienedioate-ralkyl or alkoxyalkyl. furnarate adducts give similarly valuable plasticized polyvinyl chloride compositions. Thus by employing 40 parts by weight of the 1:2 diamyl 8,12- eicosadienedioate-diethyl fumarate adduct or'of a 1:1 di-- methyl (non-conjugated) docosadienedioate-bis(Z-ethylhexyl) fumarate adduct or of the 1:4 diethyl (non-conju gated) tetracosadien'edioate-3-propoxypropyl fumarate adduct with 60 parts by weight of polyvinyl chloride'or lt'was foundito .have a saponification alkoxyalkyl radicals of from 1 to 8 carbon atoms, Y is an aliphatic, non-conjugated diolefinic hydrocarbon radical of-from l8 to 28 carbon atoms, and n is a number of from 1 to 6.

2. An adduct of the formula v 1 ROOC-Y--COOR HC 0 O-R] I omcoo-R in which R denotes an alkyl radical of from 1 to 8 carbon atoms and Y is an aliphatic, non-conjugated diolefinic hydrocarbon radical of from 18 to 28 carbon atoms, and n is a number of from 1 to 6.

, 3. An adduct of the formula R-OOC-Y-COO-R CHzCOO-R n in which R denotes an alkyl radical of from 1 to 8 carbon atoms, Y is an 8, l2-di0lefinic C hydrocarbon radical, and n is an integer of from 1 to 6.

.4. An adduct of the formula in which R is an alkyl radical of from 1 to 8 carbon atoms, Y is an 8, 12-diolefinic C hydrocarbon radical and n is an integer of from 1 to 6.

5.. An adduct of the formula I Omoooomomo 013,011, in which R is an radical of from 1 to 8 carbon atoms,

Y is an 8, 12-diolefinic C hydrocarbon radical and n is an integer of from 1 to 6.

6. An adduct of the formula in which Y is an 8, 12-dio1efinic C hydrocarbon radical and n is an integer of from 1 to 6.

7. An adduct of the formula CH (CH2):O O C-YC O (CHDaCH;

[CH0 0 O CHrCHrO CHlCHg] H 0 0 0 011201120 CHnCH;

in which Y is an 8, l2-diolefiriic C hydrocarbon radical and n is an integer of from 1 to 6.

8. The method which comprises heating at a temperature of 100 C. to 300 C. a alkadienedioate of the formula in which R is an alkyl radical of from 1 to 8 carbon atoms and Y is an aliphatic, non-conjugated, diolefinic hydrocarbon radical of from 18 to 28 carbon atoms with a fumarate of the formula ZOOC.CH CH.COOZ

in which Z is selected from the class consisting of alkyl and alkoxyalkyl radicals of from 1 to 8 carbon atoms and recovering from the resulting reaction product an adduct of the formula R o 0 c-Y-o 0 0 R 211110 0 OZ],.' in which R, Y and Z are as herein defined and n is a number of from 1 to 6.

9. The method which comprises heating at a temperature of from 100 C. to 300 C. a dialkyl fumarate having from 1 to 8 carbon atoms in each alkyl radical with a nonconjugated, dialkyl alkadienedioate having from 1 to 8 carbon atoms in each alkyl radical and from 20 to 30 carbon atoms in the acyl portion of the dioate, and re covering from the resulting reaction product an adduct of the formula R-O OCYC0 0-3. 43110 0 0-R [bmcoo-R]. in which R denotes an alkyl radical of from 1 to 8 carbon 6 atoms and Y is an aliphatic, non-conjugated diolefinic hydrocarbon radical of from 18 to 28 carbon atoms, and n is a number of from 1 to 6.

10. The method which comprises heating at a temperature of from C. to 300 C. di-n-butyl fumarate with di-n-butyl 8, l2-eicosadienedioate and recovering from the resulting reaction product an adduct of the formula H 0 0 O OHgCHzO CH2OH31 in which Y is an 8, 12-diolefinic'C hydrocarbon radical and n is an integer of from 1 to 6.

12. A resinous composition comprising a vinyl chloride polymer plasticized with an adduct of the formula JHCOOZ [t l H, 0 0 oz in which R is an alkyl radical of from 1 to 8 carbon atoms, Z is selected from the class consisting of R and alkoxyalkyl radicals of from 1 to 8 carbon atoms, Y is an aliphatic, non-conjugated diolefinic hydrocarbon radical of from 18 to 28 carbon atoms, and n is a number of from 1 to 6.

13. A resinous composition comprising a vinyl chloride polymer plasticized with the adduct defined in claim 2.

14. A resinous composition comprising polyvinyl chloride plasticized with the adduct defined in claim 2.

15. A resinous composition comprising polyvinyl chloride plasticized with the adduct defined in claim 5.

16. A resinous composition comprising polyvinyl chloride plasticized with the adduct defined in claim 6.

17. A resinous composition comprising polyvinyl chloride plasticized with the adduct defined in claim 7.

No references cited. 

12. A RESINOUS COMPOSITION COMPRISING A VINYL CHLORIDE POLYMER PLASTICIZED WITH AN ADDUCT OF THE FORMULA 